Certain non-terpenoid juvenile hormone mimicking compounds

ABSTRACT

1. A COMPOUND OF THE FORMULA   R1-CH(-R)-NH-CO-CO-NH-CH2-CH2-N(-CH2-CH3)-CO-CO-NH-   CH(-R1)-R   IN WHICH R IS ALKYL HAVING 1 TO 4 CARBON ATOMS AND R1 IS ALKYL HAVING 1 TO 4 CARBON ATOMS WITH THE PROVISO THAT R AND R1 TAKEN TOGETHER HAVE NO MORE THAN 6 CARBON ATOMS.

United States Patent U.S. Cl. 260-482 P 5 Claims ABSTRACT OF THEDISCLOSURE 1O Compounds having the formula t t i N N R tor W Y H O k O Rin which R and R are alkyl and their use in controlling insects.

This invention relates to the use of certain novel chemical compoundseffective in combatting noxious insects.

A new class of selective compounds has been found which exerts adisrupting influence upon the normal development of insects. Suchcompounds impede the metamorphosis of larvae to pupae and pupae toadults resulting in the formation of abnormal members of the treatedspecies which may also be non-viable or sterile. This ultimately leads,indirectly at least, to the destruction of a pest population.

The compounds of the present invention are believed to have the furtheradvantages that they are non-toxic to warm blooded animals and arehighly effective in controlling insects at low dosages.

One embodiment of the present invention is concerned with novelpesticidal compositions.

In another embodiment, the invention is concerned with the activepesticidal component of such compositions.

In still another embodiment, the invention is concerned with a processfor controlling insects by hindering or impeding the metamorphosis andreproduction of the insects.

The compounds of the present invention that are useful in controllinginsects are those having the formula ice The compounds of this inventioncan be prepared by the following reactions:

Reaction (1) O 0 [5 H: (CZHs) 3N 2C2H5O C1 HzN CHZCHINH t? i? CZH5O NHCHCHzN J0 02H;

Reaction (2) Preferably reaction No. 1 is carried out in a solvent suchas methylene chloride, with stirring by slowly adding a solution of thealkyl oxalyl chloride in a solvent such as methylene chloride to asolution of the diamine in the presence of an acid acceptor, such astriethylamine, at a temperature around 0 C., followed by stirring tocomplete the exothermic reaction. The reaction product is recovered byconventional techniques such as washing with water, followed byseparating the organic layer, washing again and drying with anhydrousMgSO Finally, the solvent is filtered and removed by vacuum stripping.

Preferably, the reaction is carried out using one mole amounts of thediamine reactant, and two moles of the oxalyl chloride reagent.Although, a slight excess of a reactant can be used.

Preferably, reaction No. 2 is carried out by reacting the product ofreaction No. 1, the bis-ethyloxalyl compound, with the desired amine.The excess amine acts as a solvent. An exothermic reaction occurs uponmixing. When the reaction subsides, the desiredcompound is obtained bystripping the volatile components.

Preparation of the compounds of this invention is illustrated by thefollowing specific examples.

EXAMPLE I N-ethyl-N,N'-bis (ethyloxa1yl)-ethylene diamine 8.8 grams (0.1mole) N-ethyl-ethylene diamine, 10.1 grams (0.1 mole) triethylamine andmilliliters CH Cl are mixed in a 3-neck flask equipped with a droppingfunnel, a mechanical stirrer and placed in an ice bath. 27.2 grams (0.2mole) ethyl oxalyl chloride dis solved in 50 milliliters CH Cl is slowlydropped into the mixture under stirring causing an exothermic reaction.The reaction mixture is stirred for two hours.

The reaction product is recovered by adding 200 milliliters water withstirring. The separated organic layer is washed again with 200 ml.water, followed by drying with MgSO The organic phase is filtered andstripped to yield 17.3 grams of the desired product. N 1.4670. N.M.R.analysis confirm the structure.

EXAMPLE II N-ethyl-N,N'-bis(isopropyloxamyl)-ethylene diamine 3.0 gramsof the product obtained in Example I are mixed with millilitersisopropylarnine. After an exothermic reaction subsides, the resultingmixture is refluxed for V2 hour, cooled and stripped in vacuum. 3.4grams of the desired compound is obtained. N.M.R. analysis confirms thestructure.

EXAMPLE III N-ethyl-N,N'-bis(scc-butyloxamyl)-ethylene diamine 2.5 gramsof the product obtained in Example I are mixed with 15 milliliterssec-butylamine. After an exothermic reaction subsides, the resultingmixture is refl-uxed for A hour, cooled and stripped in vacuum. 28 gramsof the desired product is obtained. M.P. 92-105 C. N.M.R. analysisconfirms the structure.

The product of reaction No. 1 is a novel compound useful for preparingthe compounds of this invention. Other esters are also useful for thesame purpose and have the formula:

wherein R is alkyl having 1 to 6 carbons, cyclohexyl or phenyl. They areprepared by using the appropriately substituted oxalyl chloride in placeof ethyl oxalyl chloride in reaction No. 1.

INSECTICIDAL EVALUATION TEST The degree of activity of a candidatecompound to hinder or impede the metamorphosis of insects is measured bytreating the penultimate larval stage of a representative insect withthe compound and examining it after its last molt toward the adult formfor retention of immature features.

Specifically, yellow mealworm, Telebrio molitor, L., larvae aremaintained at 28 C. and 40' percent humidity on a diet of bran flakes.Prepupae are collected from the culture and kept in separate containers.The pupae collected once daily, are 1-25 hours old at the time oftreatment. By means of a syringe, suitable amounts of candidatecompounds in 0.5 or 1.0 al. of acetone are applied to the venter of Tenebrio molitor, L. pupae. Treated pupae are maintained at 28 C. and 40percent humidity until the adults emerged (usually within 6-8 days).Emerged adults are graded as positive, negative, or dead. To beconsidered a positive response, the presence of typical pupal cuticle,urogomphi, gin trap, and abnormal wings, etc., are required. For eachtest, 1 group of 10 pupae was used.

The dose of a candidate compound per pupa that is needed to give apositive response in the above insecticidal evaluation test for 5 of the10 pupae is determined. Table I shows these doses under the column EDsu,the ED being an abbreviation for effective dose, for the compoundsprepared in Examples II and III.

TABLE I Compound of: ED ag/ pupa Example II .01 Example III .005

The compounds of this invention are generally embodied into a formsuitable for convenient application. For example, the compounds can beembodied into pesticidal composition which are provided in the form ofemulsions, suspensions, solutions, dusts, and aerosol sprays. Ingeneral, such compositions will contain, in addition to the activecompound, the adjnvants which are found normally in pesticidepreparations. In these compositions, the active compounds of thisinvention can be employed as the sole pesticide component or they can beused in admixture with other compounds having similar utility. Thepesticide compositions of this invention can contain, as adjuvants,organic solvents, such as sesame oil, xylene range solvents, heavypetroleum, etc., water; emulsifying agents; surface active agents; talc;pyrophyllite; diatomite; gypsum; clays; propellants, such asdichlorodifluoromethane, etc. If desired, however, the active compoundscan be applied directly to feedstuffs, seeds, etc., upon which the pestsfeed. When applied in such a manner, it will be advantageous to use acompound which is not volatile.

The compounds can also be combined with baits in a conventional manner.

The precise manner in which the pesticide compositions of this inventionare used in any particular instance will be readily apparent to a personskilled in the art. Gen erally, the active pesticide compound will beembodied in the form of a liquid composition, for example, an emulsion,suspension, or aerosol spray. While the concentration of the activepesticide in the present compositions can vary within rather widelimits, ordinarily the pesticide compound will comprise not more thanabout 50 percent by weight of the composition. Prefereably, however, thepesticide compositions of this invention Will be in the form ofsolutions or suspensions containing about 0.1 to 1.0 percent by weightof the active pesticide compound.

What is claimed is:

1. A compound of the formula in which R is alkyl having 1 to 4 carbonatoms and R is alkyl having 1 to 4 carbon atoms with the proviso that Rand R taken together have no more than 6 carbon atoms. 2. The compoundof Claim 1 in which R is methyl and R is methyl.

3. The compound of Claim 1 in which R is ethyl and R is methyl.

6 4. The compound of the formula FOREIGN PATENTS m 1,560,828 3/1969France 260561 K R20 NHCHCHN H LORRAINE A. WEINBERGER, Primary Examiner 5n wherein R is alkyl having 1 to 6 carbons, cyclohexyl or KILLOSAsslstant Exammer phenyl.

5. The compound of Claim 4 wherein R is ethyl.

260479 S, 561 K; 424320 References Cited 10 UNITED STATES PATENTS3,037,036 5/1962 Fierce 260561 K

1. A COMPOUND OF THE FORMULA